W+Co+C(碳黑)制备板状晶硬质合金及其性能研究

采用经球磨扁平化处理的W粉末为原料,添加适量Co、C(碳黑)、成型剂及纳米W粉制备板状晶硬质合金,研究了烧结温度、时间和添加纳米W粉,对板状晶硬质合金显微组织结构和性能的影响。结果表明,球磨预处理中颗粒W粉末可获得扁平化程度高的薄片状W粉末,以其为原料制备的WC-12%Co(质量分数)板状晶合金相对密度达97%,合金硬度呈现出明显的各向异性;添加纳米W粉或提高烧结温度、延长烧结时间,均有利于压坯烧结收缩致密化,生成更多的板状WC晶粒。     

纳米钨/碳化钨粉末的形貌遗传特性及其对粉末均匀性的影响

为研究氧化钨的形貌结构对纳米钨粉末制品均匀性的影响,用X射线衍射分析仪和电子扫描电镜对普通黄钨在660℃下还原的过程产物进行了分析、观测。同时分别以普通黄钨和强力球磨分级处理的细黄钨为原料,采用经优化的工艺条件制备出了纳米W、WC粉末,并对粉末及其快速烧结体的显微组织结构进行了观察、分析。结果表明,不同形貌结构原料制备的纳米W、WC粉末,均呈现出不同程度的形貌结构遗传特性,强力球磨分级处理所获细黄钨颗粒细小、形貌结构疏松,更容易制备出结构较疏松,分散性较好的纳米W、WC粉末。     

W粉粒径和烧结温度对一步法制备WC-10%Co硬质合金组织性能的影响

等离子球磨“碳化烧结一步法”制备WC-Co硬质合金有利于板状晶WC的形成和形态控制。本文进一步研究了等离子球磨W-C-Co复合粉末的组织演变,着重考察原始W粉粒径和烧结温度对WC-10%Co硬质合金组织、性能的影响。结果表明,等离子球磨使W颗粒显著呈片状,并增加其中位错等缺陷,提高粉末中的变形储能,同时增加了W/C反应界面,均有利于WC板状晶的生成;随着原始W粉粒径增加,等离子球磨所制备的层片状聚集体的片径越大,其生成的板状WC晶粒也越大,板状WC晶粒的定向排列程度也越高;随着烧结温度增加,WC晶粒的长径比和板状WC晶粒的定向排列程度有所提高。当原始W粉粒径为2.5μm、烧结温度1 440℃时,所制备的WC-10%Co硬质合金样品垂直于压制方向截面的横向断裂强度、硬度和断裂韧性分别为3 542 MPa、14.896 GPa、16.73 MPa·m^1/2;平行于压制方向截面的硬度和断裂韧性为13.975 GPa、15.06 MPa·mm^1/2。     

纳米晶W粉和W-Ni-Fe预合金粉的制备

采用高能球磨法制备纳米晶W粉和W-Ni-Fe预合金粉，研究了不同的球磨材质包括硬质合金球(CCB)、钨球(TAB)和球磨转速、球料比及球磨时间等条件对球磨后粉末性能的影响。利用XRD，TEM和EDX分析球磨后粉末的晶粒尺寸、晶格畸变、形貌、结构变化及颗粒成分变化。结果表明：高能球磨法可制得10nm～80nm的W粉和W-Ni-Fe预合金粉，纳米级颗粒含量达80％以上。相同材质的钨球制得的纳米粉末综合性能较好。球磨过程中，粉末保持颗粒状结构，纳米级粉末颗粒形状最终趋于等轴化。     

原料形貌特性和高温梯度碳化工艺对纳米WC粉末及其WC-Co合金均匀性的影响

采用不同氧化钨原料,通过氢还原、高温碳化工艺制备纳米W、WC粉末,研究了氧化钨形貌特性对纳米W、WC粉体形貌、均匀性的影响.择优选取了高比表面特制蓝钨(SBTO),并结合新型高温梯度碳化工艺制备了纳米碳化钨粉末,研究了新型高温梯度碳化工艺对纳米WC粉体特性及超细晶WC-Co硬质合金性能的影响.通过比表面测定仪、费氏粒度...     

以蓝钨为原料制取的粗颗粒W粉、WC粉特性的研究

本文从粉末粒度分布、微观结构以及对合金性能的影响等三方面探讨了以蓝钨为原料制取用颗粒W粉、WC粉的特性。结果表明，从W粉、WC粉的粒度分布曲线来看，蓝钨原料与黄钨原料没有什么本质区别，要制取粒度分布比较平坦、没有尖峰的粗颗粒W粉和粒度分布曲线不出现双峰的粗颗粒WC粉不能靠选择原料种类来解决；用扫描电镜观察W粉、WC粉的微观形貌时发现，用黄钨为原料制的W粉、WC粉颗粒表面存在明显微孔，而这一现象在以蓝钨为原料制得的W粉、WC粉中没有发现；与黄钨相比，以蓝钨为原料制得的WC－Co、WC－Co－Ni硬质合金具有较好的综合性能。     

两步碳化制备纳米WC粉末及其合金性能

研究了两步碳化工艺对氢还原/碳化制备的纳米WC粉末及其WC-Co合金性能的影响。结果表明,WC粉末的晶粒聚集和异常粗大颗粒主要是由于碳化初期钨颗粒因烧结合并增粗,而钨粉碳化不完全主要是由于碳化后期的温度偏低,利用先低温碳化后高温碳化的两步碳化工艺不仅能够有效抑制纳米颗粒烧结合并增粗,而且可以使钨粉充分碳化,得到颗粒细小、均匀,W2C含量极少的WC粉末;采用1120℃碳化加1180℃碳化的两步碳化工艺制备出的138 nm的WC粉末,W2C含量少于0.5%(质量分数),以其为原料制备的WC-Co烧结体显微组织结构均匀,为超细晶硬质合金,综合性能优良,洛氏硬度HRA高达93.7,抗弯强度高达4380 MPa。     

原料粉末形貌对纳米W/WC粉末均匀性的影响

以不同钨酸盐前驱体制备的黄钨(YTO)、紫钨(VTO)和细黄钨(AYTO)为原料,在五带控温管式炉中于560⁷60℃氢还原约300 min获得纳米W粉,通过干磨搅拌配碳将纳米W粉和粉状碳黑粉末混合均匀,然后置于通氢钼丝炉中在1 180℃碳化获得纳米WC粉,并制备了W-30%Cu、WC-30%Cu(质量分数)复合材料烧结体,研究了原料粉末形貌对W、WC粉末的均匀性的影响。通过比表面测定仪和费氏粒度仪测定了粉体的比表面和粒度,用扫描电镜(SEM)观察了粉末的形貌和烧结体的显微组织结构。结果表明,不同形貌的原料制备的纳米W和WC粉末的均匀性不同,钨酸盐(B)制备的细黄钨(AYTO)相成分单一,颗粒细小,具有疏松、多孔形貌结构,以其为原料所获纳米W粉、WC粉末夹粗少,均匀性好,晶粒聚集少。     

掺钨钴粉的特征研究

研究了钨掺杂对Co－W粉末结构和形貌的影响，钨掺杂是在制备Co－W合金粉的前驱体的过程中实现的。用X-射线衍射分析粉末的相成分，通过扫描电镜观察粉末的微观结构。实验结果表明，Co中固溶的W阻止钴由面心立方结构向密排六方结构转变；W含量增加时，粉末中会析出Co3W相；W阻碍Co－W粉末间的烧结，W含量越大，Co－W粉的粒度就越小。     

氧化钨的形貌结构对纳米WC粉末均匀性的影响

研究了在传统氢还原工艺制备纳米碳化钨粉末过程中不同氧化钨的形貌结构对纳米W/WC粉末均匀性的影响,并对粉末及其WC-Co烧结体的性能进行了表征。结果表明,用具有疏松、多孔形貌结构的细小氧化钨颗粒更容易制备出结构较疏松、分散性较好的纳米W粉和WC粉。晶粒聚集和异常粗大颗粒的产生,主要与碳化过程中团聚纳米钨粉颗粒因烧结合并增粗有关。     

Preparation of ultrafine tungsten powders by in-situ hydrogen reduction of nano-needle violet tungsten oxide

Ultrafine tungsten powders with a grain size below 0.5 μm are key raw materials for fabricating ultrafine cemented carbides. Conventional hydrogen reduction technique has been utilized to prepare the ultrafine tungsten powders. In the present work, highly pure nano-needles of violet tungsten oxide (WO_2.72) were reduced by dry hydrogen. Nucleation and growth of the metallic tungsten in the early stage of hydrogen reduction have been studied by XRD, FESEM and HRTEM. Mechanism of formation of nano-size tungsten powders is proposed and a concept of in-situ hydrogen of the nano-needle WO_2.72 is presented. Empirical relations between an average diameter of nano-needle WO_2.72 and an average particle size of the resultant tungsten powders in both stage of nucleation and industrial conduction have been established. These empirical relations could be a reasonable guidance for suitably choosing the raw materials of nano-needle WO_2.72 to prepare ultrafine tungsten powders. It has been determined that the BET special surface areas of the in-situ hydrogen-reduced tungsten powders with the average particle size of 0.2 μm and 0.3 μm, which were produced from the raw nano-needle WO_2.72 powders with the average diameter of 60 nm and 80 nm, are 6.03 m²/g and 4.65 m²/g, and the oxygen contents are 0.35% and 0.29%, respectively.     

EFFECTS OF SIZE COMBINATION AND CONTACTING STATE OF RAW POWDER PARTICLES ON SPARK PLASMA SINTERED ULTRAFINE CEMENTED CARBIDES

本文采用亚微米WC粉和纳米Co粉、亚微米WC粉和高能球磨后具有纳米晶组织的微米级Co粉这两种具有不同粒径匹配的混合粉末作为原料粉末，利用放电等离子烧结（SPS）技术制备超细晶WC-10Co硬质合金。对不同原料粉末的SPS过程及烧结试样的显微组织和性能进行了系统的对比分析。实验结果表明，以两种混合粉末为原料均获得了平均晶粒尺寸在200nm以下的超细硬质合金材料，其中，采用亚微米WC粉和高能球磨的微米级Co粉利用SPS技术制备的材料相对密度达到98%以上，硬度达到HRA94.5，断裂韧性达到13.50MPa•m1/2，表明具有优良的综合性能。而采用亚微米WC粉和纳米Co粉利用SPS技术制备出的超细晶硬质合金的组织均匀性和性能较差。根据SPS技术的特殊烧结机理，对采用不同粒径匹配和结合状态的WC和Co混合粉末的SPS致密化机制进行了分析。     

中国超细晶硬质合金及原料制备技术进展

超细晶硬质合金是WC晶粒度≤0．5μm的硬质合金,这类合金具有高强度和高硬度的优异性能。目前由超细晶硬质合金制备的高效刀具已经广泛用于航空航天、核能、汽车、发电设备、新能源和电子通讯等现代制造业。主要对中国超细晶硬质合金原料（例如超细碳化钨粉、钴粉、复合粉）和超细晶硬质合金制备技术、性能及表征方法作了系统的阐述。最后对超细晶硬质合金制备技术进行了展望。     

Effects of fine WC particle size on the microstructure and mechanical properties of WC-8Co cemented carbides with dual-scale and dual-morphology WC grains

Dual-scale and dual-morphology WC grained WC-8Co cemented carbides comprising triangular or hexagonal fine WC grains and plate-like coarse WC grains were synthesized by vacuum sintering using Co, flaky graphite, WC, and coarse W as the starting materials. The effects of fine WC particle sizes on microstructure, relative densities, and mechanical properties of the dual-scale and dual-morphology WC grained cemented carbides were investigated. The results revealed that the growth of plate-like coarse WC grains was further promoted with the decrease in the particle size of the added fine WC; hence, their aspect ratio increased. In addition, added fine WC led to the separation of plate-like coarse WC grains so as to break their oriented arrangement and prevent their face contact; hence, plate-like coarse WC grains were completely covered by the Co binder phase. Moreover, the addition of smaller particle size of fine WC contributed to more uniform Co binder phase. When 0.4-μm WC powders was added, the aspect ratio of plate-like coarse WC grains was greater than that of plate-like WC grained cemented carbides without the addition of fine WC. The dual-scale and dual-morphology WC grained cemented carbides by adding 0.4-μm fine WC exhibited good comprehensive mechanical properties, with a transverse rupture strength of 3645 MPa, a Rockwell hardness of 91.5 HRA, and a fracture toughness of 12.3 MPa∙m^1/2.     

机械活化-反应热处理制备纳米晶WC-Co复合粉末的研究

以W、C、Co为原料粉末,经机械活化-反应热处理工艺制备纳米晶WC-Co复合粉末。实验发现活化粉末的固相反应具有以下特征:反应温度低,反应速度快。在800℃热处理时已有大量的WC生成。在850℃保温25minW2C就完成了向WC的转化。经900℃保温35min制备了晶粒尺寸为30.5nm的WC-Co复合粉末。     

A short and facile process to synthesize WC-Co cemented carbides

WC-Co cemented carbides are widely used in the fields of military, aerospace, mining and cutting industry etc. In this paper, a new two-step method for the preparation of WC-Co cemented carbides was proposed. First, the mixture of yellow tungsten trioxide (WO₃) and cobaltic oxide (Co₂O₃) were reduced by carbon black to remove all the oxygen. Then, the carbothermic reduction products were precisely mixed with an appropriate amount of carbon black to directly prepare WC-Co cemented carbides. The effects of C/WO₃ ratio on the phase composition, morphological evolution, particle size and mechanical properties of products are investigated. The experimental results revealed that when the C/WO₃ molar ratio was above 2.7, all oxygen in the raw material mixture were removed by carbon black and a mixture of W₂C and η-phase were obtained after the first step of carbothermic reduction at 1150 °C for 2 h; then, the mixture of carbothermic reduction product and an appropriate content of carbon black was compacted, and the green compact was first carbonized at 1200 °C for 2 h and then sintered at 1450 °C for 4 h to prepare cemented carbides. With the increase of C/WO₃ ratio at the first stage, the content of η-phase with a low melting point increased, which resulted in the large grain size of WC in the finally prepared cemented carbide. Compared with the traditional method of preparing cemented carbides, the cemented carbides prepared by the current method showed a higher hardness and toughness. Furthermore, the addition of a proper content of the VC in the second stage can significantly inhibit the grain growth of WC and further increase the hardness of cemented carbides.     

Synthesis and processing of nanocrystalline tungsten carbide: Towards cemented carbides with optimal mechanical properties

Nanocrystalline tungsten carbide has been obtained by reduction/carburization at low temperature from precursors obtained by freeze-drying of aqueous solutions. Nanocrystalline WC powders with a adequate content of carbon were mixed with submicrometric Cobalt powder (12 wt.%), obtained by same synthesis method, and sintered in vacuum furnace. The cemented carbides fabricated from experimental powders were compared with both commercial ultrafine and nanocrystalline WC-12Co mixtures consolidated by the same route. The synthesised powders were characterized by X-ray powder diffraction, elemental analysis and scanning and high resolution transmission electron microscopy. On the other hand, density, microstructure, hardness and fracture toughness together with X-ray diffraction analysis of the sintered materials were evaluated. The cemented carbides obtained from synthesised powders exhibited a WC platelet-based homogeneous microstructure. This anisotropic growth might be due to the presence of stacking faults parallel to the basal plane in the starting WC powder, which would promote the defect-assisted preferential growth. These materials showed excellent mechanical properties, with a superior hardness/fracture toughness combination compared to materials prepared from commercial mixtures.